Origin of the 330 nm absorption band and effect of doping Yb in LiYF4 crystals

The electronic structures of LiYF₄ (YLF) crystals containing F color center (YLF-F) and Yb doped YLF crystals (Yb³⁺:YLF, Yb²⁺:YLF) are systematically studied within the framework of the density functional theory. The calculated results indicate that the 330 nm absorption band originates from the F center in YLF crystals. Thus the doping of Yb³⁺ can weaken the 330 nm absorption band by competing with F vacancies in capturing free electrons arising after γ-irradiation and change to Yb². By analyzing the lattice relaxation and the electronic structure of YLF containing Yb²⁺, we can reasonably believe that once Yb²⁺ is formed in YLF crystal, its compensating hole will turn out to be shared by two F⁻ nearest to Yb²⁺ forming a diatomic fluoride molecular ion () perturbed by Yb²⁺, or to say V_F color center. According to the molecular-orbital linear combination of atomic orbital (MO-LCAOs) theory, compared to the alkali halides, e.g. LiF, the in V_F center in LiYF₄ peaks at about 340 nm, which is in agreement with the experimental results.